Plasticized cellulose derivative compositions



' it'is associated during manufacture.

Patenteci Aug. i9, 3%41 PLASTICIZED CELLULOSE DERIVATIVE EOMJPO SITIONS Joseph B. Dickey and James B. Normington, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing.

6 Claims.

This invention relates to compositions of matter in which cellulose derivatives, such as cellulose acetate, cellulose nitrate or cellulose ethers,

are combined or mixed with other substances, such as a compatible plasticizer, and a common solvent for both, .with or without other useful addition agents, so that the resulting product will have properties such as will make the composition highly advantageous for use in the plastic and analogous arts, such for instance, as the manufacture of wrapping sheets, photographic film, artificial silk, varnishes orlacquers, and the like.

One object of this invention is. to produce a composition of matter which may be made into permanently transparent, strong and flexible sheets'or films of desired thinness which are'substantially waterproof, are unaflected by ordinary photographic fluids and possess the desired properties of a support for sensitive photographic coatings. Another object of our invention is to produce a composition which is capable of easy and convenient manipulation in the plastic and analogous arts, such as in the manufacture of sheets, films, artificial silk filaments, varnishes, lacquers and the like, and to. proinjured by, the substances or surfaces with which Other objects will become apparent to those skilled in the art to which this invention pertains.

While cellulose acetate, nitrates and others have been known for decades it has also been known that to utilize them in the various plastic arts it is necessary to mix therewith suchplasticizing or conditioning agents as camphor. castor oil, triphenyl phosphate, monochlornaphthalene or the like. Certain of these and other addition agents are also added for the purpose oi. reducing the inflammability of the product. Plastic inducing agents, such as the higher alcohols and their esters, are sometimes also added. Similarly, addition compounds of various kinds have been employed to increase flexibility, transparency, toughness, and other properties which will enhance the value of the resulting product. Addition products for the same or similar purposes are also added to cellulose acetates, nitrates and ethers to prepare them for use in the other plastic arts, such as in the manufacture of lacquers, varnishes, artificial silk filaments, moulded compounds and the like. While the plasticizers or other addition agents heretofore discovered have had their utility in the art, the increasing use to which cellulose derivatives Application December 16, 1938, Serial No. 248,200

. duce a composition which will not injure, or be Compound Formula Boiling range Triettlclatigolamino trl- N(ClHAOGOCHI)L--- 197-201" 0.]16 mm.

ace a i Triothanolamine di- (CzHrOCOCHs):

acetate monoptopionato. N 215-223 0.]25 mm.

C:H4OCOC :H Triethunolaminedi- CQHQOCOCHI proplonatemonoacetote. N- 184-187 0J5 mm.

Trithanolamino tri- N(C|H4OCOC:Hs)z. 218223 C./2l mm.

propionato. Til'liethagilamino tri- N(C:H40G0CsH )1 210-220 C./23mm. exoa have been put and the increasing number oi desirable properties required of the cellulose derivative for most purposes has made the discovcry of new and economical plasticizers or other addition agents a matter of considerable impor- 1 tance to the art.

We have discovered that valuable properties may be induced in and/or contributed to compositions containing cellulose derivatives. such as cellulose acetate, by adding thereto as plasticizing compounds organic esters of tertiary amines, said esters having the formula:

where R, R R and R are the same or different substituted or unsubstituted alkyl, alkylene, cycloalkyl, aryl or-heterocyclic groups and n is 1, 2, 3, etc. This class of compounds is compatible with cellulose derivatives and particularly compatible with cellulose acetate in the percentages hereinafter given,

Typical examples of compounds which, in accordance with our invention, we have found to be valuable plasticizers, are given in the following table.

DERIVATIVES OF I'I'RIETHANOLAMINE Examples of the preparation of the typical com- I pounds of this type are as follows:

PREPARATION or TRIETHANOLAMINE TRIACETATE Q parts of triethanolamine are treated with 320 parts acetic anhydride. Heat is given of! and the solution is refluxed for two hours. 400 parts of the triacetate are obtained by'distillagion, having a boiling point at 16 mm. of 198- Fith until Pnnraaa'rron or Tamnanommna Tarraorrona'm Seven equivalents of propionyl chloride are added slowly to two parts triethanolamine and the whole heated on the water bath until nomore hydrogen chloride is given off. The excess acid halide is neutralized with alkali and the triethanolamine tripropionate obtained by distillation in good yields-boiling point 218-220 C./21

PREPARATION or TRIETHANOLAMINE 'DIACETATE Monornorrona'ra A mixture of 150 parts triethanolamine, 75

parts propionic acid, 125 parts acetic acid, 5.

' obtained, having a boiling point at 25 mm. of

In the following examples and description we have set forth several of the preferred embodiments of our invention, but they are included merely for purposes of illustration and not as a limitationthereof.

Example 7 Parts Cellulose butyr y can C;H1C-OC:HHOC|HN o v C1114 Propylene chloride, 300' Ace 100 Example 8 a Parts Cellulose acetate butyrate 100 Triethanolamine benzoate 15 Triphenyl thiophosphate 8 Ethylene chloride 400 Methanol 100 Example 9 Parts Ethyl cellulose 100 chm-0cm rr-mm-oo-cm-oom CHCH: 2 5

Composition of matter prepared as above described may be deposited upon any suitable fllm forming surface .to form a film'or sheet, as is well known to those skilled in the art. A film modified Schopper fold-tester (commonly used for such purposes) without breaking and that evenafter being subjected for a considerable number of days to air maintained at a temperature of 65 C. the film still maintains flexibility (in contrast to almost complete lack of flexibility where no plasticizer is used) demonstrating that the film will withstand ordinary usage satisfactorily for many years. The sum'total of the above advantageous properties of a product produced from our new composition is considerably in excess of that of products produced with what have previously been regarded as the better plasticizers. g

In order that those skilled in this art may better understand our invention we would state, by way of illustration; that for the manufacture of photographic film or other sheets our new composition of matter may be compounded as 1 follows: 100 parts of acetone soluble cellulose Example 1 Parts Cellulose acetate 100 Triethanolamine acetate; Acetone 400 Example 2 Parts Cellulose acetate s 'Triethanolamine butyrate 20 Acetone 300 Methanol 100 Example 3 1 v Parts Cellulose acetate 100 Triethanolamine hexoate 30 Ethylene chloride 300 Dioxane s 100 Example4 Parts Cellulose acetate 100 Triethanolamine laurate 20 Triphenyl phosphate 20 Ace 300 Ethyl acetate 100 Example 5 I Parts Cellulose acetate propionate 100 Butyl phthaiate 20 Tripropanolamine mono butyrate diacetate..- 30 Propylene chloride 200 Ethyl lac 100 Acetone 100 Example 6 Parts Cellulose nitrate 100 Dibutyl-p-hydroxyethylamine tetrahydrofuroa Ester g 40 Ethyl acetate 200 Toluene 100 100 acetate, 1. e. cellulose acetate containing from 38% to 42% acetyl radical, approximately, is dissolved with stirring at atmospheric temperature in 300 to 500 parts, preferably 400 parts, by weight, of acetone. added from 5-50 parts by weight, of any one of the above plasticizers, it being found preferable to employ approximately 30 to 10 parts thereof. I he amount of plasticizer may be decreased or increased, depending upon whether it is desired to decrease or increase, respectively the properties which this plasticizer contributes to the To this solution may be I acetate and our new plasticizers may also occur to those skilled in this art. In like manner our plasticizers may be compounded with other single or mixed organic esters of cellulose, such as cellu cation flied of even date herewith, compositions of matter similar to those described herein may be employed in the manufacture of artificial silk by the dry spinning method. With a proper coagulating bath they may be employed for wet spinning. It may be desired to employ a composition of diiferent viscosity or evaporation characteristics, but this is a mere matter of changing the solvent proportion or adding evaporation retardants or other high or intermediate boiling constituents, as has been well known in O the 'art for morethan a decade.

. Our novel plasticizers may be employed also with advantage in connection with a number of the known lacquer and varnish formulas with which it may be found to be compatible. In such cases the plasticizer is usually first put into solution with the cellulose derivative solution and. if non-solvents are added. only to such an extent as will not precipitate the derivative from solution. Also the plasticizer is usually employed in larger amounts, such as from 50 to 60 parts, in compounding lacquers. Other uses within the scope of our invention will also suggest themselves to those skilled in the art and are to be included within the scope of the claims appended hereto.

What we claim is: s

1. A composition of matter comprising cellulose acetate and triethanolamine tripropionate.

2. A composition of matter comprising cellulose acetate and triethanolamine triacetate.

3. A composition of matter comprising cellulose acetate and triethanolamine hexoate. s

4. A composition of matter comprising a cellulose ester and an organic ester of a tertiary amine alcohol containing at least one and not more than three hydroxy groups completely esterified with a monocarboxylic organic acid and having the general formula;

I R 00 m N-R R'] where R, R R and R are organic radicals. selected from the group consisting of alkyl, alkylene, c'ycloalkyl, aryl and heterocyclic groups and wherein n is a positive integer not over three.

5. A composition of matter comprising cellulose acetate and an organic ester of a tertiaryr amine alcohol containing at least one and not more than three hydroxy groups completely esterifled with a monocarboxylic organic acid and having the general formula:

N m u where R, R R, and R are organic radicals selected from the group consisting of alkyl, a1- kylene, cycioalkyl, aryl and heterocyclic groups and wherein n is a positive integer not over three- 6. A composition of matter comprising 10 0 parts of a cellulose esterand 5-50 parts or .n organic ester of a tertiary amine alcohol containing at least one and not more than three hydroxy groups completely esterifled with a monocarboxylic organic acid and having the general formula:

R 00 R1 [e 14 r where R, R R and R. are organic radicals selected from the group consisting of alkyl, al-

kylene, cycloalkyl, aryl and heterocyclic groups and wherein n is a 

